Binderless Molecular Sieve Catalyst and a Preparation Method Thereof

ABSTRACT

The present invention relate to a binderless molecular sieve catalyst and a process for preparing the same, which are mainly useful for solving the problems of the current catalysts, such as lower activity, less pore volume and worse diffusivity. The present invention relates to a novel binderless molecular sieve catalyst, comprising, based on the weight of the catalyst, 90-100 wt. % of a molecular sieve, 0-10 wt. % of a binder, and 0-10 wt. % of an anti-wear agent, wherein said catalyst has a pore volume of 0.1-0.5 ml/g, an average pore diameter of 50-100 nm, and a porosity of 20-40%; the anti-wear agent is selected from the rod or needle-like inorganic materials having a length/diameter ratio of 2-20. Said catalyst has the advantages of higher activity, greater pore volume, larger average pore diameter and porosity, and better diffusivity, and well solves said problems and can be used for the industrial preparation of binderless molecular sieve catalysts.

TECHNICAL FIELD

The present invention relates to a binderless molecular sieve catalystand a process for preparing the same.

BACKGROUND ART

Due to the uniform and regular porous structure, greater specificsurface area and higher thermal stability, better shape-selectivecatalytic performance and adsorption performance, zeolite molecularsieves are widely applied in the fields such as petrochemical industryand the like. When molecular sieves are used for industrial catalysis,100% molecular sieves generally cannot be made into the catalyst for theindustrial process. Because of worse binding property and too smallparticle size, molecular sieves still have a strength of lower than 20Newtons even if press-molded, so that they cannot be molded to form thecatalyst directly applied in the industrial process. In addition, themanufacturing cost of molecular sieves is generally higher. If 100%molecular sieves are used as the industrial catalyst, the operation costof the industrial process increases. The industrial process generallyrequests that the catalyst has a certain shape and strength so as to beadapted to the industrial reactor. As for a fixed-bed reactor, thecatalyst does not need to be moved after installation, but the catalystshall have a certain anti-crush strength to avoid breakage due to impactduring the loading process and to prevent the catalyst loaded in thelower part from breakage under pressure. The breakage and pulverizationof the catalyst may result in an increase of the pressure drop in thedevice, abnormal reaction behavior, or product composition change, whichare disadvantageous to the target reaction process. As for a fixed-bedreactor, because of circular flow and turbulent motion of the catalystper se in the reactor, friction and collision between the catalystparticles, between the catalyst and the reactor wall, between thecatalyst and the regenerator wall, between the catalyst and the heaterwall, between the catalyst and the flow pipe wall all will grind anddamage the catalyst so as to escape from the reaction system in a finepowder form. Such fine powder will pollute the environment, and increasethe use-cost of the catalyst. Thus, no matter whether the molecularsieves are applied in a fixed-bed reactor or a fluidized-bed reactor, abinder is necessary for a catalyst composition formed by molecularsieves and carrier materials. Such molecular sieve composition has thecatalytic activity, selectivity, stability, shape and strength, andmeets the requirements on the catalyst during the industrial process.

Since a binder shall be added for forming the molecular sieves, and thebinder wraps the molecular sieves in the molded catalyst, the effectiveavailability of molecular sieves decreases, so as to result in a lowerspecific surface area and a lower activity of the catalyst. Randomporous structure of the binder causes the difficulty of the dispersionof the reaction materials and product in the catalyst, and carbondeposit easily occurs, so as to have effect on the service life of thecatalyst. The conversion of the binder in the catalyst into theeffective component molecular sieve can overcome said problems andimprove the activity and diffusivity of the catalyst.

The binderless molecular sieve catalyst involves converting the binderadded during the molding of the zeolite molecular sieve catalyst intothe effective component of the molecular sieve, making the wholecatalyst containing no binder component and maintaining a betterstrength of the catalyst. In the binderless molecular sieve catalyst,the binder is completely converted to the molecular sieve component,which increases the molecular sieve content in a unit volume of thecatalyst, so as to improve the activity and handling capacity of thecatalyst. Meanwhile, since the catalyst contains no binder, it solvesthe problems that the effective availability of the molecular sieve isreduced because the binder wraps the molecular sieves, and that thebinder blocks up the pore channel of the molecular sieves, so as togreatly increase the effective availability and carbon depositresistance thereof.

Generally, a binderless molecular sieve catalyst means that the bindercontent in the catalyst is less than 10%.

US6509290 discloses a process for preparing a molecular sieve catalyst,which contains molecular sieve-containing attrition particles and virginmolecular sieve, the attrition particles having been recycled from acatalyst manufacture process or from a reaction system. Such processcomprises mixing together molecular sieves, virgin binder and filler,spray-dried attrition particles or agglomerates, and non-virginattrition particles from a reaction system, drying the mixture to forman end product catalyst particles. In order to increase the strength ofthe catalyst particles, the attrition particles substantially contain nocoke.

US6153552 studies a process for preparing a molecular sieve catalyst,comprising mixing together molecular sieves and an alumina sol which isprepared in a solution and maintains a pH value of 2-10, spray-dryingand calcining such mixture at high temperature, to form a catalystresistant to attrition.

CN1791463 discloses a process for preparing a molecular sieve catalyst,comprising mixing together molecular sieve, liquid, and an effectivehardening amount of a dried molecular sieve catalyst to form a slurry,drying the slurry and then calcining to form a catalyst resistant toattrition.

Although some patents have involved the process for preparing afluidized-bed catalyst, the abrasion resistance thereof is lower andneeds to be further improved.

Generally, molecular sieves are prepared by the hydrothermal synthesis,showing a powder form, having no strength, and being easy to lose. Evenif they are molded by compression, the strength thereof is also lessthan 20 Newton, so that they cannot be applied directly. The molecularsieves shall be extruded or spray-molded by adding a binder during theindustrial or laboratory application. During the molding process of theconventional molecular sieve catalyst, the weight of the binder to beadded is not less than 40% of the total weight of the catalyst. Althoughthe molded catalyst has a certain strength, it has a reduced effectiveavailability and worse activity and diffusivity.

CONTENTS OF THE INVENTION

The first problem to be solved by the present invention is to provide anovel binderless molecular sieve catalyst, which has the advantages ofhigher activity, greater pore volume, larger average pore diameter andporosity, and better diffusivity.

The second problem to be solved by the present invention is to provide anovel preparation process for the binderless molecular sieve fixed-bedcatalyst as mentioned in the above first technical problem to be solved.Such process has the advantages of simple preparation, lower cost andenvironmental protection.

The third problem to be solved by the present invention is to provide anovel preparation process for the binderless molecular sievefluidized-bed catalyst as mentioned in the above first technical problemto be solved. Such process has the advantages of simple preparation,lower cost and environmental protection.

In a first aspect of the present invention, in order to solve the firstproblem above, the present invention comprises a binderless molecularsieve catalyst, comprising, based on the weight of the catalyst, 90-100wt. % of a molecular sieve, 0-10 wt. % of a binder, and 0-10 wt. % of ananti-wear agent, wherein said catalyst has a pore volume of 0.10-0.52ml/g, an average pore diameter of 50-100 nm, and a porosity of 20-40%;the anti-wear agent is selected from the rod or needle-like inorganicmaterials having a length/diameter ratio of 2-20.

In one preferred embodiment, the content of the binder in thebinderless-type catalyst may be less than 5 wt. %, preferably less than2 wt. %, more preferably less than 1 wt. %, based on the weight of thecatalyst.

In one preferred embodiment, the catalyst has a pore volume of 0.15-0.3ml/g, an average pore diameter of 50-70 nm, a porosity of 20-30%. Inanother preferred embodiment, the catalyst has a pore volume of 0.31-0.5ml/g, an average pore diameter of 71-100 nm, a porosity of 31-40%.

In one preferred embodiment, the molecular sieve in the binderlessmolecular sieve catalyst comprises at least one selected from the groupconsisting of ZSM-5, ZSM-23, ZSM-11, mordenite, Y zeolite, β zeolite,MCM-22, MCM-49, MCM-56, ZSM-5/mordenite, β zeolite/mordenite, ZSM-5/βzeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/βzeolite/mordenite, ZSM-5/β zeolite/Y zeolite and ZSM-5/Yzeolite/mordenite.

In one preferred embodiment, the anti-wear agent is at least oneinorganic material selected from the group consisting of asbestos,ceramic fiber, glass fiber, and wollastonite mineral, wherein theanti-wear agent has a length of 1-100 μm and a length/diameter ratio of3-10 and is in an amount 2-10 wt. % based on the weight of the calcinedend product of the catalyst.

In one preferred embodiment, the binder is at least one selected fromthe group consisting of silica sol and aluminum sol.

In a second aspect of the present invention, in order to solve thesecond problem above, the present invention comprises a process forpreparing a binderless molecular sieve catalyst, comprising the steps of

-   -   a) based on the weight of the molded and calcined catalyst,        mixing 10-80 wt. % of a molecular sieve, 0.1-20 wt. % of an        induction material, 0-20 wt. % of an aluminum compound and 10-80        wt. % of silica, molding and drying to obtain a molded catalyst        precursor mix I, wherein the weight percent of the aluminum        compound in the mix I is less than that of silica;    -   b) crystallizing the mix I at 100-200° C. in water vapor or        template vapor for 10-300 h, to obtain a binderless molecular        sieve catalyst precursor;    -   c) drying the catalyst precursor, and calcining at 400-700° C.        for 1-10 h to obtain a binderless molecular sieve catalyst;        wherein the induction material is at least one selected from the        group consisting of i) oxides or hydroxides of the elements of        Group IA or IIA of the Periodic Table of Elements, or salts of        weak acids thereof, ii) at least one selected from the group        consisting of carbonates, bicarbonates, oxalates, citrates and        ammonium salts of the elements of Group IA or IIA of the        Periodic Table of Elements; the aluminum compound is at least        one selected from the group consisting of aluminum salts,        aluminum oxides, hydrous oxides of aluminum and hydroxides of        aluminum.

In one preferred embodiment, the molecular sieve is at least oneselected from the group consisting of ZSM-5, ZSM-23, ZSM-11, mordenite,Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/mordenite, ZSM-5/βzeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/βzeolite/mordenite, ZSM-5/β zeolite/Y zeolite and ZSM-5/Yzeolite/mordenite.

In one preferred embodiment, the template is at least one selected fromthe group consisting of ammonia, ethylene diamine, triethylamine,n-butylamine, hexanediamine, tetrapropylammonium bromide ortetrapropylammonium hydroxide, tetraethylammonium hydroxide,tetraethylammonium bromide and hexamethyleneimine, and is in an amountof 5-200 wt. % based on the weight of the mix I.

In one preferred embodiment, the element of Group IA is at least oneselected from the group consisting of sodium and potassium.

In one preferred embodiment, the element of Group IIA is at least oneselected from the group consisting of magnesium and calcium.

In one preferred embodiment, the salt of weak acids is at least oneselected from the group consisting of bisulfate, sulfite, hydrosulfite,phosphate and biphosphate.

In one preferred embodiment, the ammonium salt is at least one selectedfrom the group consisting of ammonium carbonate, ammonium bicarbonate,ammonium citrate, ammonium oxalate, ammonium sulphate, ammoniumbisulphate, ammonium sulphite, ammonium bisulphite, ammonium phosphate,ammonium hydrogen phosphate and diammonium phosphate.

In one preferred embodiment, the molecular sieve in step a) is in anamount of 20-70 wt. %, based on the weight of the molded and calcinedcatalyst.

In one preferred embodiment, the induction material in step a) is in anamount of 0.5-10 wt. %, based on the weight of the molded and calcinedcatalyst.

In one preferred embodiment, the aluminum compound in step a) is in anamount of 1-15 wt. %, based on the weight of the molded and calcinedcatalyst.

In one preferred embodiment, silica in step a) is in an amount of 30-70wt. %, based on the weight of the molded and calcined catalyst.

In one preferred embodiment, the crystallization is carried out at120-200° C. for 20-100 h.

In one preferred embodiment, during the molding process of step a), atleast one pore-expanding agent selected from the group consisting ofmethyl cellulose, polyvinyl alcohol, sesbania powder, dissolvable starchand carbon nano-tube is added in an amount of 0.1-2 wt. %, based on theweight of the molded and calcined catalyst.

In one preferred embodiment, the catalyst prepared according to theaforesaid aspect has a strength of 60-200 newton, preferably 100-180newton.

The binderless catalyst prepared according to the aforesaid aspect ispreferably useful in the reactions of preparing low carbon olefins bycatalytic cracking of naphtha and by methanol dehydration.

Upon extrusion, the catalyst precursor mix I is present in a form of along strip solid having a tangential plane in a cylindrical form and adiameter of 0.5-2 mm, and is dried and crushed into short cylindricalcatalyst strips having a length of 5 mm per particle for convenience ofcrystal conversion treatment and evaluation. The mechanical strength ofthe catalyst in the present invention is measured and calculatedaccording to such shape. In addition, the catalyst precursor mix I canalso be made as required into a cellular form, a clover form, a hollowtubular or a spherical form, and the strength standard is extra.

Among the characterizing means of the binderless catalyst, XRD is usedto determine the phase contained therein, and the content of each phase;the scanning electron microscope is used to observe the crystalconversion of the binder and the morphology of the produced molecularsieve. Upon crystal conversion, the binder content is determined by theXRD phase quantification and the binder content in the scanning electronphotomicroscope. The Si—Al ratio in the catalyst is determined by thechemical analysis method. The strength of the catalyst is determined bymeasuring the crushing strength of the calcined catalyst on thecompression testing machine. The catalyst to be measured has a particlediameter of 1.5 mm and a length of 5 mm. The catalyst is horizontallydisposed on the testing machine to determine the maximum pressuresuffered when the catalyst is crushed. The crushing strength of 10particles of the catalyst is measured to take the average. The porevolume, average pore diameter and porosity of the catalyst aredetermined by the mercury injection method.

In a third aspect of the present invention, in order to solve the thirdproblem above, the present invention comprises a process for preparing abinderless molecular sieve catalyst, comprising the steps of

-   -   (a) homogeneously mixing a molecular sieve, a binder, a        dispersant having the induction action, a liquid medium, an        optional pore-expanding agent, an optional substrate material,        and an optional anti-wear agent to form a suspension, wherein        the dispersant is selected from the group consisting of i) salts        of weak acids of the elements of Group IA or IIA of the Periodic        Table of Elements, or ii) carbonates, bicarbonate, oxalates and        citrates of ammonium;    -   (b) high velocity (e.g. 6,000-30,000 rpm) shearing and diffusing        to control the particle size of the materials in the suspension        within 0.1-5 μm;    -   (c) spray-drying said suspension to form a microsphere catalyst        precursor I;    -   (d) calcining such microsphere catalyst precursor I at        300-700° C. for 1-10 h to obtain a catalyst precursor II;    -   (e) crystallizing the catalyst precursor II at 100-300° C. in        water vapor or template vapor for 10-240 h, to obtain a catalyst        precursor III; and    -   (f) calcining such microsphere catalyst precursor III at        400-700° C. for 1-10 h to obtain an end product of the catalyst.

In one preferred embodiment, the molecular sieve is at least oneselected from the group consisting of ZSM-5, ZSM-23, ZSM-11, mordenite,Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/mordenite, ZSM-5/βzeolite, ZSM-5/β zeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite,ZSM-5/β zeolite/mordenite, ZSM-5/β zeolite/Y zeolite and ZSM-5/Yzeolite/mordenite, and is in an amount of 20-80 wt. % based on theweight of the calcined end product catalyst.

In one preferred embodiment, the binder is at least one selected fromsilicasol and aluminum sol, and is in an amount of preferably 2-50 wt. %based on the weight of the calcined end product of the catalyst.

In one preferred embodiment, the substrate material is at least oneselected from the group consisting of kaolin, calcined kaolin,diatomite, bentonite, argil and clay, and is in an amount of 0-50 wt. %based on the weight of the calcined end product of the catalyst.

In one preferred embodiment, the pore-expanding agent is at least oneselected from the group consisting of methyl cellulose, polyvinylalcohol, sesbania powder, dissolvable starch and carbon nano-tube, andis in an amount 0.1-5 wt. % based on the weight of the molecular sievein the calcined end product of the catalyst.

In one preferred embodiment, the salt of weak acids is at least oneselected from the group consisting of bisulphate, sulphite,hydrosulfite, phosphate and biphosphate.

In one preferred embodiment, the dispersant is at least one selectedfrom the group consisting of tri-ammonium citrate, ammonium oxalate,ammonium carbonate and ammonium bicarbonate, and is in an amount 0.01-5wt. % based on the weight of the molecular sieve in the calcined endproduct of the catalyst.

In one preferred embodiment, the anti-wear agent is at least oneinorganic material selected from the group consisting of asbestos,ceramic fiber, glass fiber, and wollastonite mineral, wherein theanti-wear agent has a length of 1-100 μm and a length/diameter ratio of3-10 and is in an amount 2-10 wt. % based on the weight of the calcinedend product of the catalyst.

In one preferred embodiment, the liquid medium is distilled water.

In one preferred embodiment, the solids content of the suspension instep (a) is preferably 10-50%.

In one preferred embodiment, the particle size of the materials iscontrolled to be 0.1-2 μm by using a high velocity shearing or cyclicemulsification method.

In one preferred embodiment, the spray-drying is conducted under theconditions of an inlet temperature of 180-350° C., an outlet temperatureof 100-180° C., a centrifugal rotational speed of 5,000-15,000 rpm, anda cyclone pressure difference of 0.5-1.0 KPa at the outlet.

In one preferred embodiment, after the spray-dried catalyst is calcinedat high temperature, the particles of the catalyst precursor II have anaverage particle size of 50-90 μm, a specific surface area of 100-300m²/g, an average pore diameter of 1-20 nm, a density of 0.6-1.2 g/ml andan abrasion index of 0.005-1.2 wt. %/h (when an anti-wear agent isadded, the abrasion index may reach 0.001 wt. %/h).

In one preferred embodiment, the template is at least one selected fromthe group consisting of ammonia, ethylene diamine, triethylamine,n-butylamine, hexanediamine, tetrapropylammonium bromide ortetrapropylammonium hydroxide, tetraethylammonium hydroxide,tetraethylammonium bromide and hexamethyleneimine, and is in an amountof 5-200 wt. % based on the weight of the molded and calcined catalystprecursor II.

In one preferred embodiment, the crystallization is carried out at120-200° C. for 20-200 h.

Among the characterizing means of the binderless catalyst, XRD is usedto determine the phase contained therein, and the content of each phase;the scanning electron microscope is used to observe the crystalconversion of the binder and the morphology of the produced molecularsieve. Upon crystal conversion, the binder content is determined by theXRD phase quantification and the binder content in the scanning electronphotomicroscope. The Si—Al ratio in the catalyst is determined by thechemical analysis method. The abrasion index of the catalyst isdetermined by the solid granular catalyst abrasion tester, whereinnitrogen gas is sued as the carrier gas. The pore volume, average porediameter and porosity of the catalyst are determined by the mercuryinjection method. The specific surface areas of the catalyst precursorII and end product catalyst are determined by the nitrogen temperatureprogrammed desorption.

In the second aspect of the present invention, the environment andmaterial proportion adapted to the growth of molecular sieves arecontrolled by using as the crystal seed the molecular sieves added intothe molded catalyst, so as to nucleate the binder and to make it growunder the common induction of the crystal seed and induction materialsand only in an environment of water vapor. As a result, the binder isconverted into the effective component of molecular sieves, so as toobtain a binderless molecular sieve catalyst and to achieve the objectof simplicity and environmental protection. In the produced binderlessmolecular sieve catalyst, the binder may be in an amount of less than 2wt. %, preferably less than 1 wt. %, or even there is no binder (i.e.the catalyst merely contains molecular sieves and an optional anti-wearagent). Since the molecular sieve content in the catalyst per unitvolume is higher, the active site number in the catalyst per unit volumeis greater, so that the binderless molecular sieve catalyst has a higheractivity. Since the crystal grains of the binderless catalyst molecularsieves obtained by crystal conversion are interlaced with each other,and closely integrated with each other, the catalyst strength may reach120-200 newton per grain, preferably higher than 180 newton per grain.Since a template can be omitted during the crystal conversion, thetechnological process of crystal conversion is simple andenvironmentally friendly. Some salts of weak acids, carbonates,oxalates, citrates or ammonium salts are added during the preparation ofthe binderless molecular sieve catalyst, so as to have the inductionaction during the crystal conversion and to produce some macropores dueto decomposition of the salts and thus have the function of thepore-expanding agent. Thus the produced catalyst has the advantages ofhigher pore volume, greater average pore diameter and porosity andbetter diffusivity. The fixed-bed catalyst produced according to thepresent invention can be used in the reaction for producing propylene bycatalytic cracking of naphtha. The yield of dienes of ethylene andpropylene is preferably higher than 53%, more preferably higher than55%.

In the third aspect of the present invention, at least one selected fromthe group consisting of, e.g. tri-ammonium citrate, ammonium oxalate,ammonium carbonate and ammonium bicarbonate is added to make thecomponents in the catalyst being homogeneously dispersed and difficultto agglomerate. By high velocity emulsification and shearing, thesuspension is not easy to stratify or precipitate, and the preparedcatalyst has a smooth surface and a high sphericity. When heated, thesesalts of weak acids are easy to decompose so as to produce gases, whichis advantageous to increasing the porosity, average particle diameterand surface area of molecular sieves. When the dispersant is selectedfrom the salts of weak acids of the elements of Group IA or IIA, suchdispersant has a certain low acidity. Even if heated and decomposed, thedispersant may produce certain basic oxides. The presence of these basicoxides is advantageous to convert the binder and substrate componentsinto the molecular sieve components. Without template or molecularsieves, these suitable ingredients may be converted into molecular sievecomponents in a water vapor environment.

In a preferred embodiment, the catalyst has a better diffusivity and ahigher activity due to the addition of at least one pore-expanding agentselected from the group consisting of methyl cellulose, polyvinylalcohol, sesbania powder, dissolvable starch and carbon nano-tube duringthe preparation of the catalyst. Since the formulated slurry ishomogeneous, and the substances can closely bind to each other, thephases of the prepared catalyst are closely integrated with each other,so that the end product catalyst obtained thereby has a higher abrasionstrength. Since the formulated slurry is homogeneous, the components andsubstances in the catalyst can closely bind to each other by addingslender crystal anti-wear agents having a higher strength in thepreferred embodiment, so that the end product catalyst obtained therebyhas a higher abrasion strength and an abrasion index as high as 0.001wt. %/h (e.g. 0.001-0.01 wt %/h), and achieves a better technicaleffect. The fluidized-bed catalyst produced according to the presentinvention can be used in the reaction for producing propylene bycatalytic cracking of naphtha. The yield of dienes of ethylene andpropylene may be higher than 50%.

Unless otherwise noted, the percent in the present invention refers tothe weight percent.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the XRD spectrum of the binderless ZSM-5 catalyst preparedaccording to Example 1.

FIG. 2 shows the scanning electron microscope graph of the binderlessZSM-5 catalyst prepared according to Example 1.

FIG. 3 shows the scanning electron microscope graph of the binderlesscatalyst prepared according to Example 2.

FIG. 4 shows the scanning electron microscope graph of the catalystprepared according to Example 50.

FIG. 5 shows the scanning electron microscope graph of the binderlessZSM-5 catalyst prepared according to Example 61.

EMBODIMENTS

The present invention is further illustrated by the following examples,but is not limited to the examples.

Example 1

60 g of ZSM-5 molecular sieve having a Si—Al ratio (molecular ratio,hereinafter inclusive) of 30 was added to 40 g of 40 wt. % of asilicasol, homogeneously mixed and stirred. 10 ml of 1 mol/l of sodiumhydroxide solution was then added, homogeneously mixed and stirred, andextrusion-molded. The molded catalyst was dried at 80° C. for 3 h, fedinto an autoclave the inner bottom of which contains water. The catalystwas not brought in contact with liquid water, then sealed in theautoclave and disposed in an oven, crystallized at 170° C. for 60 h,taken out, water-washed twice, oven-dried at 120° C. in an oven for 3 h,calcined in a muffle furnace at 400° C. for 2 h and at 550° C. for 3 h,to obtain a binderless ZSM-5 catalyst. The results of the preparedcatalyst are shown in Table 3, wherein the XRD spectrum thereof shown inFIG. 1 which shows a pure ZSM-5 phase. The scanning electron microscopegraph of the prepared catalyst is shown in FIG. 2 which shows pure ZSM-5crystal grains, almost without any amorphous binder. The amount ofamorphous binder was determined to be 0.2%, and the crushing-resistantstrength of the catalyst sample was determined to be 150 newton pergrain.

Example 2

According to the method in Example 1 of CN101428233A, a mixed crystalmolecular sieve of ZSM-5/β zeolite having a Si—Al ratio of 40 wasprepared. 60 g of ZSM-5/β zeolite was added to 40 g of 40 wt. % of asilicasol, homogeneously mixed and stirred. Then 2 g of potassium oxidewas added, homogeneously mixed and stirred, and extrusion-molded. Themolded catalyst was dried at 80° C. for 3 h, fed into an autoclave theinner bottom of which contains water. The catalyst was not brought incontact with liquid water, then sealed in the autoclave and disposed inan oven, crystallized at 165° C. for 80 h, taken out, water-washedtwice, oven-dried at 120° C. in an oven for 3 h, calcined in a mufflefurnace at 400° C. for 2 h and at 550° C. for 3 h, to obtain abinderless ZSM-5/β zeolite catalyst, wherein the results are shown inTable 3. The XRD spectrum of the prepared catalyst shows a symbioticphase of ZSM-5 and β zeolite. The scanning electron microscope graph ofthe prepared catalyst shows a cubical shaped ZSM-5 molecular sievephase, a spherical β zeolite phase, almost without any amorphous binder,as shown in FIG. 3. The amorphous binder was in an amount of 0.5%, andthe crushing-resistant strength of the catalyst sample was determined tobe 160 newton per grain.

Examples 3-16

Mordenite having a Si—Al ratio of 20, 60 g of Y zeolite having a Si—Alratio of 10, MCM-22 having a Si—Al ratio of 40, ZSM-5/mordenitesymbiotic molecular sieve having a Si—Al ratio of 20, ZSM-5/β zeolite/Yzeolite symbiotic molecular sieve having a Si—Al ratio of 40, ZSM-5/Yzeolite/mordenite symbiotic molecular sieve having a Si—Al ratio of 20,ZSM-23 having a Si—Al ratio of 20, ZSM-11 having a Si—Al ratio of 30,MCM-49 having a Si—Al ratio of 40, MCM-56 having a Si—Al ratio of 60,ZSM-5/Y zeolite symbiotic molecular sieve having a Si—Al ratio of 20,MCM-22/mordenite having a Si—Al ratio of 40, ZSM-5/Magadiite having aSi—Al ratio of 200 and ZSM-5/β zeolite/mordenite having a Si—Al ratio of30 were respectively taken (the feedstock proportion is shown inTable 1) to prepare a binderless mordenite catalyst according to themethod in Example 1, as shown in Table 3.

Examples 17-22

The molecular sieves used in Examples 3-8 were respectively used. Duringthe molding, the pore-expanding agents selected from the groupconsisting of sesbania powder, methyl cellulose, dissolvable starch andpolyvinyl alcohol were added, wherein the feedstock proportion is shownin Table 2, and other conditions are stated in Example 1, to prepare abinderless zeolite catalyst. The results are shown in Table 3.

Example 23

The binderless catalyst prepared according to Example 1 was exchangedwith 5% of an ammonium nitrate solution three times at 90° C. in asolid:liquid (catalyst:ammonium nitrate solution) ratio of 1:10, andthen calcined at 550° C. for 3 h, to obtain a hydrogen-type binderlessZSM-5/β zeolite symbiotic molecular sieve catalyst. The activity of thecatalyst was evaluated by using the raw material C₄-C₁₀ light oilsproduced by Sinopec Shanghai Gaoqiao Company and a fixed-bed reactorhaving a diameter of 12 mm under the conditions of a reactiontemperature of 650° C., a reaction pressure of 0.02 MPa, a weight hourlyspace velocity of 1 h⁻¹, a water/feedstock oil weight ratio of 1:1. Theproduct distribution after half an hour is shown in Table 5; theethylene weight yield is 28%; the propylene weight yield is 27%; thediene weight total yield is 55% (see Table 6 for results).

Example 24

The binderless catalyst prepared according to Example 8 was exchangedwith 5% of an ammonium nitrate solution three times at 90° C. in asolid:liquid (catalyst:ammonium nitrate solution) ratio of 1:10, andthen calcined at 550° C. for 3 h, to obtain a hydrogen-type binderlessmolecular sieve catalyst. The catalyst was evaluated by using methanolas the raw material and a fixed-bed reactor having a diameter of 12 mmunder the conditions of 450° C., a weight hourly space velocity of 1h⁻¹, a water/methanol weight ratio of 1:1, a pressure of 0.02 MPa, toobtain the ethylene weight yield of 25%, and the propylene weight yieldof 45%.

Comparative Example 1

The catalyst was prepared according to the same method as Example 1,except that sodium hydroxide was not used. The results of the preparedcatalyst are shown in Table 3. According to the method of Example 23above, a hydrogen-type molecular sieve was prepared and evaluated by thesame method, and the results are shown in Table 6 below.

TABLE 1 Feedstocks Molecular sieves Aluminum compounds Inductionmaterials Water Crystallization Amount Amount Silica Amount Amounttemperature Crystallization Examples Type (g) Type (g) (g) Type (g) (g)(° C.) time (h) Example 3 Mordenite 30 aluminium 5 20 sodium hydroxide 220 170 80 sulphate Example 4 Y zeolite 50 sodium 10 10 potassium 14 4180 10 aluminate hydroxide Example 5 MCM-22 50 19 magnesium 7 10 150 150hydroxide Example 6 ZSM-5/mordenite 80 aluminium 10 15 calcium oxide 204 160 200 chloride Example 7 ZSM-5/β zeolite/Y 80 pseudo- 1 80 potassiumoxide 0.5 40 165 80 zeolite boehmite Example 8 ZSM-5/Yzeolite/ 80aluminium 5 20 potassium 0.1 20 180 60 mordenite nitrate hydroxideExample 9 ZSM-23 10 aluminium 10 80 potassium 20 40 170 240 sulphatehydroxide Example 10 ZSM-11 70 sodium 10 25 sodium hydroxide 10 20 100200 aluminate Example 11 MCM-49 10 sodium 10 15 sodium hydroxide 5 4 15080 aluminate Example 12 MCM-56 70 sodium 5 20 potassium 5 20 150 200aluminate hydroxide Example 13 ZSM-5/Y zeolite 40 sodium 5 10 sodium 5for each 20 160 40 aluminate hydroxide + potassium hydroxide Example 14MCM-22/mordenite 80 aluminium 5 20 potassium 0.1 20 180 60 nitratehydroxide Example 15 ZSM-5/Magadiite 10 aluminium 10 80 potassium 20 40170 240 sulphate hydroxide Example 16 ZSM-5/β 70 sodium 10 25 sodiumhydroxide 10 20 100 200 zeolite/mordenite aluminate

TABLE 2 Feedstocks Amount Pore-expanding Aluminum of agent compoundsInduction materials Crystallization molecular Amount Amount SilicaAmount temperature Crystallization Examples sieves (g) Type (g) Type (g)(g) Type (g) (° C.) time (h) Example 17 80 polyvinyl 1 aluminum 1 80sodium 0.5 170 80 alcohol hydroxide bisulphate Example 18 80 sesbania0.2 aluminium 5 20 sodium 0.1 180 60 powder nitrate bisulphite Example19 10 dissolvable 0.1 aluminium 10 80 potassium 20 190 240 starchsulphate phosphate Example 20 70 methyl 2 sodium 10 25 potassium 10 10010 cellulose aluminate hydrogen phosphate Example 21 10 sesbania 1sodium 10 15 potassium 5 for 150 60 powder + aluminate phosphate + eachdissolvable sodium starch bisulphate Example 22 70 sesbania 0.6 sodium 520 potassium 5 150 300 powder aluminate dihydrogen phosphate

TABLE 3 Strength of Zeolite content Binder the (wt. %) in the contentresultant Average resultant (wt. %) in the catalyst Pore pore binderlessresultant (newton volume diameter Porosity Examples catalyst catalystper grain) (ml/g) (nm) (vol. %) Example 1 99.8 0.2 150 0.34 62 32Example 2 99.5 0.5 160 0.31 51 29 Example 3 99.4 0.6 170 0.21 60 25Example 4 98.8 1.2 150 0.28 65 27 Example 5 97.9 2.1 150 0.26 64 26Example 6 100 0 190 0.3 53 22 Example 7 98.5 1.5 175 0.29 58 24 Example8 98.6 1.4 175 0.29 56 24 Example 9 95.0 5.0 80 0.31 71 30 Example 1098.4 1.6 160 0.24 54 26 Example 11 99.9 0.1 200 0.15 50 20 Example 1295.5 4.5 110 0.26 65 28 Example 13 96.1 3.9 90 0.32 69 29 Example 1498.5 1.5 175 0.19 54 27 Example 15 98.6 1.4 175 0.17 53 26 Example 1695.0 5.0 80 0.32 70 30 Example 17 98.4 1.6 160 0.17 55 28 Example 1899.9 0.1 200 0.10 49 20 Example 19 98.5 1.5 175 0.14 52 26 Example 2098.6 1.4 175 0.16 53 27 Example 21 95.0 5.0 80 0.27 70 31 Example 2298.4 1.6 160 0.19 56 26 Com. Exp. 1 62.1 37.9 70 0.08 20 11

TABLE 4 Items Data Density (20° C.) kg/m3 704.6 Distillation range 40Initial distillation range (° C.) Distillation range 160 Finaldistillation range (° C.) Saturated vapor pressure (20° C.) kpa 50.2Alkane % (wt. %) 65.2 Cyclane % (wt. %) 28.4 Alkene % (wt. %) 0.2 Arene% (wt. %) 6.2

TABLE 5 Product distribution Product weight yield (%) Methane 5.2 Ethane6.1 Ethylene 28.0 Propane 6.5 Propylene 27.0 Butane 8.7 Butene 7.6Fractions having more than 5 8.8 carbons Others 2.1

TABLE 6 Catalyst Ethylene intensity yield Propylene yield Diene yieldExamples (Newton/grain) (wt. %) (wt. %) (wt. %) Example 23 150 28 27 55Com. Exp. 1 70 24 23 47

Example 25

60 g of ZSM-5 molecular sieve having a Si—Al ratio (SiO₂/Al₂O₃ molecularmolar ratio, hereinafter inclusive) of 30, and 3.2 g of sesbania powderwere homogeneously mixed and stirred. 40 g of 40 wt. % of a silicasolwas added, homogeneously mixed and stirred. 10 ml of 1 mol/l of sodiumbicarbonate solution was then added, homogeneously mixed and stirred,and extrusion-molded. The molded catalyst was dried at 80° C. for 3 h,fed into an autoclave the inner bottom of which contains water. Thecatalyst was not brought in contact with liquid water, then sealed inthe autoclave and disposed in an oven, crystallized at 180° C. for 60 h,taken out, water-washed twice, oven-dried at 120° C. in an oven for 3 h,calcined in a muffle furnace at 400° C. for 2 h and at 550° C. for 3 h,to obtain a binderless ZSM-5 catalyst. The XRD spectrum of the preparedcatalyst shows a pure ZSM-5 phase. The scanning electron microscopegraph thereof shows pure ZSM-5 crystal grains, almost without anyamorphous binder. The amorphous binder was in an amount of 0.2%, and thecrushing-resistant strength of the catalyst sample was determined to be145 newtons per grain. By the mercury-injection method, the pore volumeis determined to be 0.38 ml/g; the average pore diameter thereof is 82nm; and the porosity thereof is 36%, as shown in Table 9.

Example 26

According to the method in Example 1 of CN101428233A, a mixed crystalmolecular sieve of ZSM-5/β zeolite having a SiO₂/Al₂O₃ molecular molarratio of 40 was prepared. 60 g of ZSM-5/β zeolite was added to 40 g of40 wt. % of a silicasol, homogeneously mixed and stirred. Then 20 ml of1 mol/l of ammonium citrate was added, homogeneously mixed and stirred,and extrusion-molded. The molded catalyst was dried at 80° C. for 3 h,fed into an autoclave the inner bottom of which contains water. Thecatalyst was not brought in contact with liquid water, then sealed inthe autoclave and disposed in an oven, crystallized at 165° C. for 80 h,taken out, water-washed twice, oven-dried at 120° C. in an oven for 3 h,calcined in a muffle furnace at 400° C. for 2 h and at 550° C. for 3 h,to obtain a binderless ZSM-5/β zeolite catalyst are shown in Table 9.The crushing-resistant strength of the catalyst sample was determined tobe 160 newtons per grain, and the amorphous binder was in an amount of0.6%. By the mercury-injection method, the pore volume is determined tobe 0.37 ml/g; the average pore diameter thereof is 80 nm; and theporosity thereof is 35%.

Examples 27-40

Mordenite having a Si—Al ratio of 20, 60 g of Y zeolite having a Si—Alratio of 10, MCM-22 having a Si—Al ratio of 40, ZSM-5/mordenitesymbiotic molecular sieve having a Si—Al ratio of 20, ZSM-5/β zeolite/Yzeolite symbiotic molecular sieve having a Si—Al ratio of 40, ZSM-5/Yzeolite/mordenite symbiotic molecular sieve having a Si—Al ratio of 20,ZSM-23 having a Si—Al ratio of 20, ZSM-11 having a Si—Al ratio of 30,MCM-49 having a Si—Al ratio of 40, MCM-56 having a Si—Al ratio of 60,ZSM-5/Y zeolite symbiotic molecular sieve having a Si—Al ratio of 20,MCM-22/mordenite having a Si—Al ratio of 40, ZSM-5/Magadiite having aSi—Al ratio of 200 and ZSM-5/β zeolite/mordenite having a Si—Al ratio of30 were respectively taken (the feedstock proportion is shown in Table7) to prepare a binderless mordenite catalyst according to the method inExample 25, as shown in Table 9.

Examples 41-46

The molecular sieves used in Examples 27-32 were respectively used.During the molding, the pore-expanding agents selected from the groupconsisting of sesbania powder, methyl cellulose, dissolvable starch andpolyvinyl alcohol were added, wherein the feedstock proportion is shownin Table 8, and other conditions are stated in Example 25, to prepare abinderless zeolite catalyst. The results are shown in Table 9.

Example 47

The binderless catalyst prepared according to Example 25 was exchangedwith 5% of an ammonium nitrate solution three times at 90° C. in asolid:liquid (catalyst:ammonium nitrate solution) ratio of 1:10, andthen calcined at 550° C. for 3 h, to obtain a hydrogen-type binderlessZSM-5/β zeolite symbiotic molecular sieve catalyst. The activity of thecatalyst was evaluated by using the raw material C₄-C₁₀ light oilsproduced by Sinopec Shanghai Gaoqiao Company (see Table 4 for thephysical property indexes of the raw materials) and a fixed-bed reactorhaving a diameter of 12 mm under the conditions of a reactiontemperature of 650° C., a reaction pressure of 0.02 MPa, a weight hourlyspace velocity of 1 h⁻¹, a water/feedstock oil weight ratio of 1:1. Theproduct distribution after half an hour is shown in Table 10; theethylene weight yield is 28%; the propylene weight yield is 28%; thediene weight total yield is 56%.

Example 48

The binderless catalyst prepared according to Example 32 was exchangedwith 5% of an ammonium nitrate solution three times at 90° C. in asolid:liquid (catalyst:ammonium nitrate solution) ratio of 1:10, andthen calcined at 550° C. for 3 h, to obtain a hydrogen-type binderlessmolecular sieve catalyst. The catalyst was evaluated by using methanolas the raw material and a fixed-bed reactor having a diameter of 12 mmunder the conditions of 450° C., a weight hourly space velocity of 1h⁻¹, a water/methanol weight ratio of 1:1, a pressure of 0.02 MPa, toobtain the ethylene weight yield of 24%, and the propylene weight yieldof 47%.

Comparative Example 2

The catalyst was prepared according to the same method as Example 25,except for that sodium bicarbonate was not used. The results of theprepared catalyst are shown in Table 9. According to the method ofExample 47 of the present invention, a hydrogen-type molecular sieve wasprepared and evaluated by the same method, and the results are shown inTable 11 below.

TABLE 7 Feedstocks Crystal- Molecular sieves Aluminum compoundsInduction materials lization Amount Amount Silica Amount Watertemperature Crystallization Examples Type (g) Type (g) (g) Type (g) Type(° C.) time (h) Example 27 Mordenite 30 aluminium sulphate 5 20 sodiumcarbonate 2 20 170 80 Example 28 Y zeolite 50 sodium aluminate 10 10potassium carbonate 14 4 180 10 Example 29 MCM-22 50 sodium aluminate 119 magnesium 7 10 150 150 carbonate Example 30 ZSM-5/ 80 aluminiumchloride 10 15 calcium citrate 20 4 160 200 Mordenite Example 31 ZSM-5/β80 pseudo-boehmite 1 80 ammonium 0.5 40 165 80 zeolite/Y bicarbonatezeolite Example 32 ZSM-5/Y 80 aluminium nitrate 5 20 ammonium 0.1 20 18060 zeolite/ carbonate Mordenite Example 33 ZSM-23 10 aluminium sulphate10 80 potassium citrate 20 40 170 240 Example 34 ZSM-11 70 sodiumaluminate 10 25 sodium oxalate 10 20 100 200 Example 35 MCM-49 10 sodiumaluminate 10 15 ammonium oxalate 5 4 150 80 Example 36 MCM-56 70 sodiumaluminate 5 20 potassium 5 20 150 200 bicarbonate Example 37 ZSM-5/Y 40sodium aluminate 5 10 sodium carbonate + 5 for 20 160 40 zeolitepotassium carbonate each Example 38 MCM- 80 aluminium nitrate 5 20ammonium bisulfate 0.1 20 180 60 22/Mordenite Example 39 ZSM-5/ 10aluminium sulphate 10 80 ammonium 20 40 170 240 Magadiite bisulphiteExample 40 ZSM-5/β 70 sodium aluminate 10 25 ammonium 10 20 100 200zeolite/ phosphate Mordenite

TABLE 8 Feedstocks Pore-expanding Aluminum Amount of agent compoundsInduction materials molecular Amount Amount Silica AmountCrystallization Crystallization Examples sieves (g) Type (g) Type (g)(g) Type (g) temperature (° C.) time (h) Example 41 80 polyvinyl 1aluminum 1 80 ammonium 0.5 170 80 alcohol hydroxide bicarbonate Example42 80 sesbania 0.2 aluminium 5 20 ammonium 0.1 180 60 powder nitratebisulphite Example 43 10 dissolvable 0.1 aluminium 10 80 ammonium 20 190240 starch sulphate citrate Example 44 70 methyl 2 sodium 10 25 ammonium10 100 10 cellulose aluminate hydrogen phosphate Example 45 10 sesbania1 sodium 10 15 ammonium 5 for 150 60 powder + aluminate phosphate + eachdissolvable ammonium starch bisulphite Example 46 70 sesbania 0.6 sodium5 20 ammonium 5 150 300 powder aluminate dihydrogen phosphate

TABLE 9 Zeolite content Binder Strength of (wt. %) in the content theresultant Average resultant (wt. %) in the catalyst Pore pore binderlessresultant (newton per volume diameter Porosity Examples catalystcatalyst grain) (ml/g) (nm) (vol. %) Example 25 99.8 0.2 145 0.38 82 36Example 26 99.4 0.6 160 0.37 80 35 Example 27 99.2 0.8 170 0.31 80 35Example 28 98.3 1.7 150 0.38 85 37 Example 29 98.9 1.1 150 0.36 84 36Example 30 100 0 180 0.35 73 32 Example 31 98.5 1.5 175 0.3 78 34Example 32 98.4 1.6 175 0.31 76 34 Example 33 95.5 4.5 80 0.51 100 30Example 34 98.3 1.7 160 0.34 94 36 Example 35 99.8 0.2 185 0.35 80 30Example 36 95.6 4.4 110 0.36 95 38 Example 37 96.5 3.5 90 0.42 99 39Example 38 98.3 1.7 175 0.39 84 37 Example 39 98.0 2.0 175 0.37 83 36Example 40 95.4 4.6 80 0.52 90 40 Example 41 98.7 1.3 160 0.37 85 38Example 42 99.9 0.1 180 0.31 89 31 Example 43 98.6 1.4 175 0.34 92 36Example 44 98.5 1.5 175 0.36 93 37 Example 45 96.0 4.0 80 0.47 100 40Example 46 98.3 1.7 160 0.39 96 36 Com. Exp. 2 63.0 37.0 60 0.08 20 10

TABLE 10 Product distribution Product weight yield (%) Methane 5.2Ethane 6.1 Ethylene 28.0 Propane 6.5 Propylene 27.0 Butane 8.7 Butene7.6 Fractions having more than 5 carbons 8.8 Others 2.1

TABLE 11 Catalyst Ethylene intensity yield Propylene yield Diene yieldExamples (n/grain) (wt. %) (wt. %) (wt. %) Example 47 145 28 28 56 Com.Exp. 2 80 23 22 45

Example 49

500 g of kaolin and 2 g of sesbania powder were homogeneously mixed.2,000 g of distilled water was then added. The mixture was highvelocity-sheared with a high velocity shearing machine at a rotatingspeed of 14,000 rpm for 30 minutes. 400 g of ZSM-5 molecular sievehaving a Si—Al molecular ratio of 30 was added, and a high velocityshearing was then conducted for another 30 minutes. 500 g of aluminumsol containing 20 wt. % of alumina was added, and a high velocityshearing continued to be conducted for another 30 minutes. 1 g oftriammonium citrate was added, and a high velocity shearing continued tobe conducted for another 30 minutes. A laser particle size analyzer wasused to determine the particle size of the suspension, wherein theaverage particle size was 2 μm. A spray-drier was used for spray-moldingunder the conditions of an inlet temperature of 240° C., an outlettemperature of 120° C., a centrifugal rotational speed of 10,000 rpm, acyclone pressure difference of 0.7 KPa at the outlet, a feeding rate of1 kg/h, to obtain a microsphere catalyst precursor I. The catalystprecursor I was calcined by the temperature programming method at 400°C. for 3 h, and at 650° C. for 3 h, to obtain a calcined, moldedcatalyst precursor II. A laser particle size analyzer was used todetermine the particle size of the calcined catalyst precursor II,wherein the average particle size was 70 μm; the nitrogen adsorption anddesorption method was used to determine the specific surface area, whichwas 310 m²/g; the average pore diameter was 3.5 nm; the density of thecatalyst was 0.8 g/ml; an abrader was used to determine the abrasionindex, which is 0.02 wt. %/h.

200 g of a calcined, molded catalyst precursor II was disposed insidethe autoclave, the bottom of which contained 50 g of water and 50 g ofethylene diamine and was separated by a screen. The catalyst wasdisposed onto the screen to keep the catalyst from liquid water. Thecatalyst was sealed in the autoclave and placed in an oven, crystallizedat 180° C. for 80 h, taken out, water-washed twice, oven-dried at 120°C. in an oven for 3 h, calcined in a muffle furnace at 400° C. for 2 hand at 550° C. for 3 h, to obtain a binderless ZSM-5 fluidized-bedcatalyst. The XRD spectrum of the prepared catalyst shows a pure ZSM-5phase. The scanning electron microscope graph thereof shows pure ZSM-5crystal grains, almost without any amorphous binder. The amorphousbinder is in an amount of 0.2%, and other results are listed in Table14.

Example 50

The same method according to Example 49 was used, except for that thetemplate ethylene diamine was not used. The scanning electron microscopeof the prepared catalyst shows a part of the binder is present, as shownin FIG. 4, wherein the amorphous binder is in a content of about 5%, andother results are listed in Table 14.

Examples 51-59

The ingredients in Table 12 and preparation conditions in Table 13 wereused, wherein silicasol contained 40 wt. % of silica, to prepare thefluidized-bed catalysts according to the method in Example 49. Theproperties of the prepared catalysts are shown in Table 13; and theresults of the prepared catalysts are shown in Table 14.

Example 60

200 g of the fluidized-bed ZSM-5 catalyst prepared according to themethod in Example 48 was disposed in a fluidized-bed reactor having aninner diameter of 50 mm. The activity of the catalyst was evaluated byusing as the raw material C₄-C₁₀ light oils produced by Sinopec ShanghaiGaoqiao Company (see Table 4 for the physical property indexes of theraw materials) under the conditions of a reaction temperature of 680°C., a reaction pressure of 0.02 MPa, a weight hourly space velocity of 1h¹, a water/methanol weight ratio of 1:1. The product distribution isshown in Table 15, wherein the ethylene weight yield is 28%; thepropylene weight yield is 22%; and the diene weight total yield is 50%.

Comparative Example 3

The catalyst was prepared according to the same method as Example 50,with the difference of using no dispersant. The results of the preparedcatalyst are shown in Table 14. The method in Example 60 was used toevaluate. The obtained ethylene weight yield is 22.5%, the propyleneweight yield of 20.3% and the diene weight total yield of 42.8%.

TABLE 12 Molecular sieve Substrate Binder Pore-expanding agentDispersant Template Amount Amount Amount Amount Amount Amount ExamplesType (g) Type (g) Type (g) Type (g) Type (g) Type (g) Example ZSM-5 400kaolin 500 Aluminum 500 cellulose 2 triammonium 1 Tetrapropyl- 30 51 solcitrate ammonium bromide Example mordenite 200 Calcined 700 Aluminum 500polyvinyl 10 ammonium 0.1 tetrapropyl- 20 52 kaolin sol alcoholbicarbonate ammonium hydroxide Example Y zeolite 500 diatomite 400Aluminum 500 sesbania 1 ammonium 10 ethylene 20 53 sol powder carbonatediamine Example β zeolite 200 bentonite 500 Aluminum 1500 dissolvable 3ammonium 30 triethylamine 10 54 sol starch oxalate Example MCM-22 400argil 400 Aluminum 1000 carbon 5 triammonium 50 Hexa- 30 55 solnano-tube citrate methylene- imine Example ZSM-5/ 100 Clay 700 Aluminum1000 dissolvable 1 triammonium 0.5 hexanedi- 20 56 mordenite sol starchcitrate amine Example ZSM-5/ 600 kaolin 200 Silica sol 1000 — —triammonium 2 ammonia 40 57 Y zeolite citrate Example ZSM-5/β 300 kaolin500 Silica sol 1000 dissolvable 20 triammonium 10 tetraethyl- 20 58zeolite starch citrate ammonium hydroxide Example ZSM-5 + 200 forKaolin + 200 for Aluminum 1000 dissolvable 5 for triammonium 2 forethylene 20 for 59 β zeolite each bentonite each sol + for starch + eachcitrate + each diamine and each Silica each sesbania ammoniumn-butylamine sol powder oxalate

TABLE 13 Conditions for spray-molding Average Specific Average poreAbrasion Particle cyclone particle size of surface area of diameter ofDensity of the index of the Solids size of centrifugal pressure Feedingthe catalyst the catalyst the catalyst catalyst catalyst contentsuspension rotational difference speed precursor II precursor IIprecursor II precursor II precursor II Examples (wt. %) (μm) speed (rpm)(Kpa) (kg/h) (μm) (m²/g) (nm) (g/ml) (wt. %/h) Example 20 2.5 10000 0.62 72 295 1 0.8 0.01 51 Example 30 3.2 6000 0.7 1 80 290 3 1.1 1.0 52Example 10 4.6 5000 0.5 2.5 100 240 5 1.2 1.2 53 Example 40 5.1 120000.4 3 65 270 3.5 0.9 1.0 54 Example 25 2.4 14000 0.6 4 60 260 2.8 0.80.5 55 Example 30 0.5 15000 0.8 5 58 280 10 0.6 0.2 56 Example 20 0.18000 0.9 2 76 260 15 1.2 0.02 57 Example 30 1.0 12000 0.6 1 70 180 100.7 0.02 58 Example 30 2.8 10000 0.5 0.5 66 100 5.4 0.8 0.08 59

TABLE 14 Zeolite Binder content (wt. %) content in the (wt. %) Averageresultant in the Pore pore binderless resultant volume diameter PorosityExamples catalyst catalyst (ml/g) (nm) (vol. %) Example 50 95.0 5.0 0.3080 26 Example 51 96.1 3.9 0.26 83 30 Example 52 96.5 3.5 0.31 82 32Example 53 95.4 4.6 0.32 80 31 Example 54 98.5 1.5 0.33 72 32 Example 5596.4 3.6 0.30 75 30 Example 56 98.0 2.0 0.28 71 28 Example 57 95.0 5.00.40 95 26 Example 58 98.1 1.9 0.29 92 29 Example 59 99.0 1.0 0.32 75 26Com. Exp. 3 96.7 3.3 0.32 82 30

TABLE 15 Product distribution Product weight yield (%) Methane 5.5Ethane 7.6 Ethylene 28.0 Propane 7.1 Propylene 22.0 Butane 8.2 Butene8.4 Fractions having more than 5 carbons 9.3 Others 3.9

Example 61

500 g of kaolin, 2 g of sesbania powder and 20 g of Wollastonite havinga length-diameter ratio of 8 were homogeneously mixed. 2,000 g ofdistilled water was then added. The mixture was high velocity-shearedwith a high velocity shearing machine for 30 minutes. 400 g of ZSM-5molecular sieve having a Si—Al molecular ratio of 30 was added, and ahigh velocity shearing was then conducted for another 30 minutes. 500 gof aluminum sol containing 20 wt. % of alumina was added, and a highvelocity shearing continued to be conducted for another 30 minutes. 1 gof triammonium citrate was added, and a high velocity shearing continuedto be conducted for another 30 minutes. A laser particle size analyzerwas used to determine the particle size of the suspension which was 2μm. A spray-drier was used for spray-molding under the conditions of aninlet temperature of 240° C., an outlet temperature of 120° C., acentrifugal rotational speed of 10,000 rpm, a cyclone pressuredifference of 0.7 KPa at the outlet, a feeding rate of 1 kg/h. Thespray-molded particles were calcined by the temperature programmingmethod at 400° C. for 3 h, and at 650° C. for 3 h. A laser particle sizeanalyzer was used to determine the calcined catalyst precursor II,wherein the average particle size was 68 μm; the specific surface areawas 305 m²/g; the average pore diameter was 3.2 nm; the density of thecatalyst was 0.9 g/ml; an abrader was used to determine the abrasionindex, which is 0.001 wt. %/h.

200 g of the calcined and molded catalyst above was disposed inside theautoclave, the bottom of which contained 50 g of water and 50 g ofethylene diamine and was separated by a screen. The catalyst wasdisposed onto the screen to keep the catalyst from liquid water. Thecatalyst was sealed in the autoclave and placed in an oven, crystallizedat 180° C. for 40 h, taken out, oven-dried at 120° C. in an oven for 3h, calcined in a muffle furnace at 400° C. for 2 h and at 550° C. for 3h, to obtain a binderless ZSM-5 fluidized-bed catalyst. The XRD spectrumof the prepared catalyst shows a pure ZSM-5 phase. The scanning electronmicroscope graph thereof as shown in FIG. 5 shows pure ZSM-5 crystalgrains. The amorphous binder is in an amount of 0.3%, and other resultsare listed in Table 19.

Examples 62-70

The ingredients and preparation conditions in Tables 16-18 were used,wherein silicasol contained 40 wt. % of silica, to prepare thefluidized-bed catalysts according to the method in Example 61. Theproperties of the prepared catalysts are shown in Table 19.

Example 71

200 g of the fluidized-bed ZSM-5 catalyst prepared according to themethod in Example 61 was disposed in a fluidized-bed reactor having aninner diameter of 50 mm. The activity of the catalyst was evaluated byusing as the raw material C₄-C₁₀ light oils produced by Sinopec ShanghaiGaoqiao Company (see Table 4 for the physical property indexes of theraw materials) under the conditions of a reaction temperature of 680°C., a reaction pressure of 0.02 MPa, a weight hourly space velocity of 1h⁻¹, a water/feedstock oil weight ratio of 1:1, to obtain the ethyleneweight yield of 27%, the propylene weight yield of 23% and the dieneweight total yield of 50%.

TABLE 16 Molecular sieve Substrate Binder Pore-expanding agent AmountAmount Amount Amount Examples Type (g) Type (g) Type (g) Type (g)Example 62 ZSM-5 400 kaolin 500 Aluminum 500 cellulose 2 sol Example 63mordenite 200 Calcined 700 Aluminum 500 polyvinyl 10 kaolin sol alcoholExample 64 Y zeolite 500 diatomite 400 Aluminum 500 sesbania 1 solpowder Example 65 β zeolite 200 bentonite 500 Aluminum 1500 dissolvable3 sol starch Example 66 MCM-22 400 argil 400 Aluminum 1000 carbon 5 solnano-tube Example 67 ZSM-5/ 100 Clay 700 Aluminum 1000 dissolvable 1mordenite sol starch Example 68 ZSM-5/Y 600 kaolin 200 Silica sol 1000 —— zeolite Example 69 ZSM-5/β 300 kaolin 500 Silica sol 1000 dissolvable20 zeolite starch Example 70 ZSM-5 + 200 for Kaolin + 200 for Aluminum1000 for dissolvable 5 for β zeolite each bentonite each sol + Silicaeach starch + sesbania each sol powder Dispersant Anti-wear agent AmountLength/diameter Amount Examples Type (g) Type ratio (g) Example 62 tri-1 wollastonite 6 10 ammonium citrate Example 63 ammonium 0.1 asbestos 102 bicarbonate Example 64 ammonium 10 ceramic 20 20 carbonate fiberExample 65 ammonium 30 glass fiber 10 10 oxalate Example 66 tri- 50wollastonite 2 5 ammonium citrate Example 67 tri- 0.5 glass fiber 10 3ammonium citrate Example 68 tri- 2 ceramic 5 1 ammonium fiber citrateExample 69 tri- 10 wollastonite 8 2 ammonium citrate Example 70 tri- 2for wollastonite + 8 and 10 5 for ammonium each ceramic each citrate +fiber ammonium oxalate

TABLE 17 Average Abrasion Average Specific pore index of Conditions forspray-molding particle surface diameter Density of the Particle Inletcentrifugal cyclone size of the area of the of the the catalyst Solidssize of tem- Outlet rotational pressure Feeding catalyst catalystcatalyst catalyst precursor content suspension perature temperaturespeed difference speed precursor precursor precursor precursor IIExamples (wt. %) (μm) (° C.) (° C.) (rpm) (Kpa) (kg/h) II (μm) II (m²/g)II (nm) II (g/ml) (wt. %/h) Example 20 2.5 240 150 10000 0.6 2 72 295 10.9 0.001 62 Example 30 3.2 180 170 6000 0.7 1 80 290 3 1.2 0.8 63Example 10 4.6 290 150 5000 0.5 2.5 100 240 5 1.3 0.5 64 Example 40 5.1300 120 12000 0.4 3 65 270 3.5 1.0 0.3 65 Example 25 2.4 350 180 140000.6 4 60 260 2.8 0.9 0.005 66 Example 30 0.5 200 100 15000 0.8 5 58 28010 0.7 0.1 67 Example 20 0.1 270 140 8000 0.9 2 76 270 15 1.3 0.005 68Example 30 1.0 240 120 12000 0.6 1 70 180 10 0.8 0.002 69 Example 30 2.8250 130 10000 0.5 0.5 66 100 5.4 0.9 0.02 70

TABLE 18 Template used therein Amount (based on the weight percent ofthe molded and calcined Crystallization Calcining catalyst temperatureCrystallization temperature Calcining Examples Type precursor) (° C.)time (h) (° C.) time (h) Example triethylamine 5 180 80 600 2 62 Exampleethylene diamine 50 300 10 500 4 63 Example hexanediamine 30 150 150 5503 64 Example tetraethylammonium 200 130 200 400 10 65 hydroxide Examplehexamethyleneimine 150 170 80 700 1 66 Example triethylamine 100 180 60600 3 67 Example tetrapropylammonium 80 190 240 550 4 68 bromide Examplehexanediamine 25 100 10 650 3 69 Example tetrapropylammonium 120 150 60450 8 70 hydroxide

TABLE 19 Zeolite content (wt. %) in the resultant Binder contentbinderless (wt. %) in the Pore volume Average pore Examples catalystresultant catalyst (ml/g) diameter (nm) Porosity (vol. %) Example 6195.0 5.0 0.30 94 35 Example 62 96.0 4.0 0.36 95 34 Example 63 97.3 2.70.33 82 31 Example 64 96.0 4.0 0.34 81 30 Example 65 95.5 4.5 0.50 92 34Example 66 98.2 1.8 0.32 84 35 Example 67 99.1 0.9 0.41 87 30 Example 6898.2 1.8 0.30 91 31 Example 69 97.5 2.5 0.33 90 34 Example 70 98.5 1.50.34 83 31

1. A binderless molecular sieve catalyst, comprising, based on theweight of the catalyst, 90-100 wt. % of a molecular sieve, 0-10 wt. % ofa binder, and 0-10 wt. % of an anti-wear agent, wherein said catalysthas a pore volume of 0.10-0.52 ml/g, an average pore diameter of 50-100nm, and a porosity of 20-40%; the anti-wear agent is selected from therod or needle-like inorganic materials having a length/diameter ratio of2-20.
 2. The binderless molecular sieve catalyst according to claim 1,characterized in that the catalyst has a pore volume of 0.15-0.3 ml/g,an average pore diameter of 50-70 mm, and a porosity of 20-30%.
 3. Thebinderless molecular sieve catalyst according to claim 1, characterizedin that the catalyst has a pore volume of 0.31-0.5 ml/g, an average porediameter of 71-100 nm, and a porosity of 31-40%.
 4. The binderlessmolecular sieve catalyst according to claim 1, characterized in that themolecular sieve in the binderless molecular sieve catalyst comprises atleast one selected from the group consisting of ZSM-5, ZSM-23, ZSM-11,mordenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56,ZSM-5/mordenite, β zeolite/mordenite, ZSM-5/β zeolite, ZSM-5/Y,MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/β zeolite/mordenite, ZSM-5/βzeolite/Y zeolite and ZSM-5/Y zeolite/mordenite.
 5. The binderlessmolecular sieve catalyst according to claim 1, characterized in that theanti-wear agent is at least one inorganic material selected from thegroup consisting of asbestos, ceramic fiber, glass fiber, andwollastonite mineral, wherein the anti-wear agent has an average lengthof 1-100 μm and a length/diameter ratio of 3-10 and is in an amount 2-10wt. % based on the weight of the calcined end product of the catalyst.6. A process for preparing a binderless molecular sieve catalystaccording to claim 1, comprising the steps of a) based on the weight ofthe molded and calcined catalyst, mixing 10-80 wt. % of a molecularsieve, 0.1-20 wt. % of an induction material, 0-20 wt. % of an aluminumcompound and 10-80 wt. % of silica, molding and drying to obtain amolded catalyst precursor mix I, wherein the weight percent of thealuminum compound in the mix I is less than that of silica; b)crystallizing the mix I at 100-200° C. in water vapor or template vaporfor 10-300 h, to obtain a binderless molecular sieve catalyst precursor;c) drying the catalyst precursor, and calcining at 400-700° C. for 1-10h to obtain a binderless molecular sieve catalyst; wherein the inductionmaterial is at least one selected from the group consisting of i) oxidesor hydroxides of the elements of Group IA or IIA of the Periodic Tableof Elements, or salts of weak acids thereof, ii) carbonates,bicarbonates, oxalates, or citrates of the elements of Group IA or IIAof the Periodic Table of Elements, or iii) at least one ammonium salts;the aluminum compound is at least one selected from the group consistingof aluminum salts, aluminum oxides, hydrous oxides of aluminum andhydroxides of aluminum.
 7. The process for preparing a binderlessmolecular sieve catalyst according to claim 6, characterized in that thetemplate is at least one selected from the group consisting of ammonia,ethylene diamine, triethylamine, n-butylamine, hexanediamine,tetrapropylammonium bromide or tetrapropylammonium hydroxide,tetraethylammonium hydroxide, tetraethylammonium bromide andhexamethyleneimine, and is in an amount of 5-200 wt. % based on theweight of the mix I.
 8. The process for preparing a binderless molecularsieve catalyst according to claim 6, characterized in that the elementof Group IA is at least one selected from the group consisting of sodiumand potassium; the element of Group IIA is at least one selected fromthe group consisting of magnesium and calcium.
 9. The process forpreparing a binderless molecular sieve catalyst according to claim 6,characterized in that the salt of weak acids is at least one selectedfrom the group consisting of bisulphate, sulphite, hydrosulfite,phosphate and biphosphate.
 10. The process for preparing a binderlessmolecular sieve catalyst according to claim 6, characterized in that theammonium salt is at least one selected from the group consisting ofammonium carbonate, ammonium bicarbonate, ammonium citrate, ammoniumoxalate, ammonium sulphate, ammonium bisulphate, ammonium sulphite,ammonium bisulphite, ammonium phosphate, ammonium hydrogen phosphate anddiammonium phosphate.
 11. The process for preparing a binderlessmolecular sieve catalyst according to claim 6, characterized in that,based on the weight of the molded and calcined catalyst, the molecularsieve in step a) is in an amount of 20-70 wt. %; the induction materialis in an amount of 0.5-10 wt. %; the aluminum compound is in an amountof 1-15 wt. %; and silica is in an amount of 30-70 wt. %.
 12. Theprocess for preparing a binderless molecular sieve catalyst according toclaim 6, characterized in that the crystallization is carried out at120-200° C. for 20-200 h.
 13. The process for preparing a binderlessmolecular sieve catalyst according to claim 6, characterized in that,during the molding process of step a), at least one pore-expanding agentselected from the group consisting of methyl cellulose, polyvinylalcohol, sesbania powder, dissolvable starch and carbon nano-tube isadded in an amount 0.1-2 wt. % based on the weight of the molded andcalcined catalyst.
 14. The process for preparing a binderless molecularsieve catalyst according to claim 1, comprising the steps of (a)homogeneously mixing a molecular sieve, a binder, a dispersant having aninduction action, a liquid medium, an optional pore-expanding agent, anoptional substrate material, and an optional anti-wear agent to form asuspension, wherein the dispersant is selected from the group consistingof i) salts of weak acids of the elements of Group IA or IIA of thePeriodic Table of Elements, or ii) carbonates, bicarbonate, oxalates andcitrates of ammonium; (b) high velocity shearing and diffusing tocontrol the particle size of the materials in the suspension within0.1-5 μm; (c) spray-drying said suspension to form a microspherecatalyst precursor I; (d) calcining such microsphere catalyst precursorI at 300-700° C. for 1-10 h to obtain a catalyst precursor II; (e)crystallizing the catalyst precursor II at 100-300° C. in water vapor ortemplate vapor for 10-240 h, to obtain a catalyst precursor III; (f)calcining such microsphere catalyst precursor III at 400-700° C. for1-10 h to obtain a end product of the catalyst.
 15. The process forpreparing a binderless molecular sieve catalyst according to claim 6 or14, characterized in that the molecular sieve is at least one selectedfrom the group consisting of ZSM-5, ZSM-23, ZSM-11, mordenite, Yzeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/mordenite, ZSM-5/βzeolite, ZSM-5/Y, MCM-22/mordenite, ZSM-5/Magadiite, ZSM-5/βzeolite/mordenite, ZSM-5/β zeolite/Y zeolite and ZSM-5/Yzeolite/mordenite, and is in an amount of 10-80 wt. % based on theweight of the molded and calcined catalyst.
 16. The process forpreparing a binderless molecular sieve catalyst according to claim 14,characterized in that the binder is at least one selected from silicasoland aluminum sol, and is in an amount of 2-70 wt. % based on the weightof the calcined end product of the catalyst.
 17. The process forpreparing a binderless molecular sieve catalyst according to claim 14,characterized in that the substrate material is at least one selectedfrom the group consisting of kaolin, calcined kaolin, diatomite,bentonite, argil and clay, and is in an amount of 0-50 wt. % based onthe weight of the calcined end product of the catalyst.
 18. The processfor preparing a binderless molecular sieve catalyst according to claim14, characterized in that the pore-expanding agent is at least oneselected from the group consisting of methyl cellulose, polyvinylalcohol, sesbania powder, dissolvable starch and carbon nano-tube, andis in an amount 0.1-5 wt. % based on the weight of the molecular sievein the calcined end product of the catalyst.
 19. The process forpreparing a binderless molecular sieve catalyst according to claim 14,characterized in that the dispersant is at least one selected from thegroup consisting of tri-ammonium citrate, ammonium oxalate, ammoniumcarbonate and ammonium bicarbonate, and is in an amount 0.01-5 wt. %based on the weight of the molecular sieve in the calcined end productof the catalyst.
 20. The process for preparing a binderless molecularsieve catalyst according to claim 14, characterized in that theanti-wear agent is at least one inorganic material selected from thegroup consisting of asbestos, ceramic fiber, glass fiber, andwollastonite mineral, wherein the anti-wear agent has an average lengthof 1-100 μm and a length/diameter ratio of 3-10 and is in an amount 2-10wt. % based on the weight of the calcined end product of the catalyst.21. The process for preparing a binderless molecular sieve catalystaccording to claim 14, characterized in that the content of thesuspension solids in step (a) ranges from 10-50 wt. %.
 22. The processfor preparing a binderless molecular sieve catalyst according to claim14, characterized in that the particle size of the materials in step (b)is controlled to be 0.1-2 μm by using the high velocity shearing orcyclic emulsification method.
 23. The process for preparing a binderlessmolecular sieve catalyst according to claim 14, characterized in thatthe spray-drying in step (c) is conducted under the conditions of aninlet temperature of 180-350° C., an outlet temperature of 100-180° C.,a centrifugal rotational speed of 5,000-15,000 rpm, a cyclone pressuredifference of 0.5-1.0 KPa at the outlet.
 24. The process for preparing abinderless molecular sieve catalyst according to claim 14, characterizedin that, after the spray-dried catalyst is calcined at high temperature,the particles of the catalyst precursor II have an average particle sizeof 50-100 μm, a specific surface area of 100-310 m²/g, an average porediameter of 1-20 nm, a density of 0.6-1.2 g/ml and an abrasion index of0.01-1.2 wt. %/h.
 25. The process for preparing a binderless molecularsieve catalyst according to claim 14, characterized in that the templateis at least one selected from the group consisting of ammonia, ethylenediamine, triethylamine, n-butylamine, hexanediamine, tetrapropylammoniumbromide or tetrapropylammonium hydroxide, tetraethylammonium hydroxide,tetraethylammonium bromide and hexamethyleneimine, and is in an amountof 5-200 wt. % based on the weight of the molded and calcined catalystprecursor II.
 26. The process for preparing a binderless molecular sievecatalyst according to claim 14, characterized in that thecrystallization is carried out at 120-200° C. for 20-200 h.